CaII Binding Regulates and Dominates the Reactivity of a Transition‐Metal‐Ion‐Dependent Diesterase from Mycobacterium tuberculosis

The diesterase Rv0805 from Mycobacterium tuberculosis is a dinuclear metallohydrolase that plays an important role in signal transduction by controlling the intracellular levels of cyclic nucleotides. As Rv0805 is essential for mycobacterial growth it is a promising new target for the development of chemotherapeutics to treat tuberculosis. The in vivo metal‐ion composition of Rv0805 is subject to debate. Here, we demonstrate that the active site accommodates two divalent transition metal ions with binding affinities ranging from approximately 50 nm for Mn^II to about 600 nm for Zn^II. In contrast, the enzyme GpdQ from Enterobacter aerogenes, despite having a coordination sphere identical to that of Rv0805, binds only one metal ion in the absence of substrate, thus demonstrating the significance of the outer sphere to modulate metal‐ion binding and enzymatic reactivity. Ca^II also binds tightly to Rv0805 (K_d≈40 nm ), but kinetic, calorimetric, and spectroscopic data indicate that two Ca^II ions bind at a site different from the dinuclear transition‐metal‐ion binding site. Ca^II acts as an activator of the enzymatic activity but is able to promote the hydrolysis of substrates even in the absence of transition‐metal ions, thus providing an effective strategy for the regulation of the enzymatic activity.     

A stereodivergent approach to substituted 4-hydroxypiperidines

A stereodivergent route toward both diastereomeric forms of functionalized 4-hydroxypiperidines has been successfully developed. This route involves biocatalytic generation of the enantiopure starting materials followed by functionalization via N-acyliminium ion-mediated CC-bond formation.     

Direct synthesis of isothiocyanates from isonitriles by molybdenum-catalyzed sulfur transfer with elemental sulfur

The direct molybdenum-catalyzed sulfuration of a variety of isonitriles with elemental sulfur or propene sulfide as sulfur donors affords the corresponding isothiocyanates in good yields and under mild reaction conditions. A catalytic cycle is suggested, in which the molybdenum oxo disulfur complex operates as the active sulfur-transferring species. A novel adduct between the isonitrile and the molybdenum complex has been characterized by X-ray analysis and its association constant determined by UV-vis spectroscopy, but this adduct appears not to be involved in the sulfur-transfer process.     

Intra-organizational Networks and Performance: A Review

Intra-organizational network research had its first heyday during the empirical revolution in social sciences before World War II when it discovered the informal group within the formal organization. These studies comment on the classic sociological idea of bureaucracy being the optimal organization. Later relational interest within organizational studies gave way to comparative studies on the quantifiable formal features of organizations. There has been a resurgence in intra-organizational networks studies recently as the conviction grows that they are critical to organizational and individual performance. Along with methodological improvements, the theoretical emphasis has shifted from networks as a constraining force to a conceptualization that sees them as providing opportunities and finally, as social capital. Because of this shift it has become necessary not only to explain the differences between networks but also their outcomes, that is, their performance. It also implies that internal and external networks should no longer be treated separately.Research on differences between intra-organizational networks centers on the influence of the formal organization, organizational demography, technology and environment. Studies on outcomes deal with diffusion and adaptation of innovation; the utilization of human capital; recruitment, absenteeism and turnover; work stress and job satisfaction; equity; power; information efficiency; collective decision making; mobilization for and outcomes of conflicts; social control; profit and survival of firms and individual performance.Of all the difficulties that are associated with intra-organizational network research, problems of access to organizations and incomparability of research findings seem to be the most serious. Nevertheless, future research should concentrate on mechanisms that make networks productive, while taking into account the difficulties of measuring performance within organizations, such as the performance paradox and the halo-effect.     

Reaktive Arsen-Heterocyclen : II. 3-Arsolene als Arsiniden-Quelle

Gas phase pyrolysis (500–600°C, 1 s) of 1-phenyl-3-arsolene, 1-phenyl-3-methyl-3-arsolene, and 1-phenyl-3,4-dimethyl-3-arsolene gives polymeric (PhAs)_x and its corresponding diene. Upon increasing the temperature, further decomposition to elemental arsenic and a mixture of aromatic hydrocarbons can be observed. If the pyrolysis is carried out with a large excess of butadiene or dimethylbutadiene, significant amounts of phenylarsinidene transfer products are formed.     

The smallest length of binary 7–dimensional linear codes with prescribed minimum distance

Let n(k,d) denote the smallest value of n for which a binary (n,k,d) code exists. Then n(k, d) was known for all d, when k ?6. All values of n(7, d) will now be presented.